Tailoring the interfacial interaction in SiC-based anode materials is crucial to the accomplishment of higher energy capacities and longer cycle lives for lithium-ion storage. In this paper, atomic-scale tunable interfacial interaction is achieved by epitaxial growth of high-quality N doped graphene (NG) on SiC (NG@SiC). This well-designed NG@SiC heterojunction demonstrates an intrinsic electric field with intensive interfacial interaction, making it an ideal prototype to thoroughly understand the configurations of electron/ion bridges and the mechanisms of interatomic electron migration. Both density functional theory (DFT) analysis and electrochemical kinetic analysis reveal that these intriguing electron/ion bridges can control and tailor the interfacial interaction via the interfacial coupled chemical bonds, enhancing the interfacial charge transfer kinetics and preventing pulverization/aggregation. As a proof-of-concept study, this well-designed NG@SiC anode shows good reversible capacity (1197.5 mAh g-1 after 200 cycles at 0.1 A g-1) and cycling durability with 76.6% capacity retention at 447.8 mAh g-1 after 1000 cycles at 10.0 A g-1. As expected, the lithium-ion full cell (LiFePO4/C//NG@SiC) shows superior rate capability and cycling stability. This interfacial interaction tailoring strategy via epitaxial growth method provides new opportunities for traditional SiC-based anodes to achieve high-performance lithium-ion storage and beyond.